Sulfur dye and process of making same.



EMILE .THEODQBE BUNDsMAN, or POINT LoMA, CALIFORNIA, assrcnoii 'ro POINT Loni. CHEMICAL COMPANY, or POINT LQMA, CALIFQRNIA, A CORPORATION or sourn DAKOTA.

HSVUL-FURY DYE Ann PnocEss OF-MAKING SAME.

,vented certain new and useful Improve- The sugars may be used in combinations, to produce coloring matters:

m'ents in --Coloring-l\1 atters and Processes of Making the Same, of which the following is a specification.

ll-have discovered that'the members of the group of chemicals known as the sugars ma be used'as color formers or color basesfin'. the nianufactureof coloring matters, either alone or in combination with other. chemicals. 1 p

a great many For instance, they will, when treated alone. with the ordinarysulfuring agents of the arts, at the pro er temperatures, produce new and valuab e coloring matters similar 'inproperties to the so-called sulfur-colors of the trade. They act, therefore, as individ-' ual colorbases or color formers. Again, they may be sulfured in connection with such other chemicals as are in themselves color formers when sulfured, and produce coloring matters distinctly different from those produced b sulfuring the sugars or such other chemica s alone, or by a mechanical mixture of the products of the separate sulfurizations. .It is evident, therefore, that by the sulfuring of a mixture of a sugar with another color forming chemical new sulfur col0ring .matters are produced. The sugars may therefore be said to play the part'of co-bases. These new co-bases ma be sulfured in connection with an unlim ted number of such other color forming chemicals, and in each instance a new coloring matter obtained; they seem, therefore, to be universal in their application, and to be properly designated as universal co-bases. They seem to oc' cupy -a "unique position in the manufacture of coloring matters, noother color base having as yet been found to have similar universal applicability. New and valuable coloring matters may furthermore be produced by sulfuring the sugars in connection with other chemicals which,-while belonging to tnefsame groups as those already described an having many analogies to such chem- .i'ca s, do not in themselves possess similar color forming properties: for example, by gulfur'ing the sugars in combination with Application filed October 7, 1905. Serial No. 281,761.

Letters Patent. Patented Sept. s, 1908.

aromatic chemicals which will not, with sulfuring agents alone, produce coloring matters. These coloring matters are different from those produced by sulfur-ing of the sugars alone.- The sugars, therefore, seem to give color forming properties to such noncolor forming chemicals. I have caused experiments to be made with a number of noncolor forming aromatic chemicals, and, in each instance, a new coloring matter has been produced. The sugars occupy a unique position in the art in this respect. I find that the best results, commercially and technically, are given by the use of grape sugar, although the other sugars, as glucose or cane sugar, give excellent results.

sugars may be used as individual color bases, and, in connection with other colorforming chemicals, as co-bases, and that they impart color forming properties to still other chemicals.

The following examples will serve to illustrate the manner in which coloring matters maybe produced from the sugars:

Example I. A sugar used as a basis with sulfur-ing agents aZ0ne.-Weigh out into a suitable iron crucible: 21 parts grape sugar, 15 parts sulfur, parts sodium sulfid. Apply heat and raise the temperaturegradually to 100 C. The sulfid will dissolve in its own water of crystallization and then dissolve the sulfur and the grape sugar. Continue raising theheat gradually until about 150 C. is reached. Heat at 140160 C. until the ingredients have formed a dry mass, which can be readily pulverized, and until a dyeing test shows that the full tinctorial power has been developed, when the color-will be formed. The substance obtained by this process is dark brown in color, and is soluble in cold Water, cold sodium carbonate solution,'a-lcohol and caustic soda solution. It will dye unmordanted cotton a fast dark brown in the usual salt bath made alkaline with soda, with '01 without the assistance of sodium sulfid. The substance may also be concentrated in the usual manner by precipitation with hydrochloric acid, the substance obtained by such concentration being dark brown in color, but insoluble in cold water, coldsodium carbonate solution, alcohol and concentrated vsulfuric acid, slowly soluble in caustic alka- -line solution, readily soluble in cold sodium sulfid solution and dyeing unmordanted cot To sum up: I have discovered that the ton a fast dark brown, in the usual salt bath madealkaline with soda, the assistance of sodium sulfid, however, being necessary in the dyeing. Variations of color ranging from the resulting substance being insoluble in a dark brown to a brown black may be ob tained by changing the details of the process. For instance, .by raising the temperature I obtain a color which is nearer a black.-

Example 11. A sugar used as a co-basis, in connection with a color form'ing chemical.- YVeigh out into a suitable crucible: 8. parts grape sugar, 12 parts sulfur, '60. parts sodium sulfid crystals. Apply heat and raise the temperature to 120 C. I After one hour at 'this temperature dissolve in water, cool, and

add 6 parts of meta-nitranilin. R aise the heat to drive off the water. Then raise the temperature gradually but steadily to 250-300' C. and heat until a dry mass is formed, which can be readily pulverized, and until a dyeing test shows that, the full tinctorial power has been developed. The process takes from seven to eight hours in all. The full tinctorial power of the color is best developed by this process, although a similar color will be produced when the meta-nitranilinis added in the beginning. The substance obtained vby this process is soluble in cold water, cold sodium carbonate solution, alcohol and caustic alkaline solution, and dyes unmordanted cotton a" fast bright yellowish brown shade in the usual alkaline 'salt bath; with or without the addition of sodium sulfid. The color may also be concentrated in the usual manner by precipitation with hydrochloric acid,

cold water, cold sodium carbonate solution,

' alcohol, and concentrated sulfuric .acid,

slowly soluble incaustic alkaline solution, and readily soluble in cold sodium sulfid solution. It dyes unmordanted cotton a fast, bright yellowish brown shade, in an alkaline salt bath with the assistance of sodium sulfid. When identically the same operation is performed without. the grape sugar, a dull greenish black alone is formed. This example illustrates a great number of syntheses of coloring matters that can be performed by. the use of these universal oobases in combination with other chemicals which are themselves color bases.- Thus, b

substituting for meta-nitranilin either metaphenylene diamin base or meta-dinitrobenzene, in the above formula, browns will be formed somewhat similar to the brown obtained from' meta-nitranilin} By using paranitrophenol a darker yellow brown is ob. Y

tained. Bi-nitrochlorb'enzol yields a valuable medium brown. 1.8 dinitro-naphthalene yields. a valuable black. Variations of temperature will produce a variation in the shade of the product. By varyingthe pro-' portions of the ingredients other variationsin color can be produced.

Example III. 4' sugar to impart color;

pulverizable forming properties to a chemical whichumier SLInLZCZ-T ctrcumstances and condtttons, 'LS not a color-fomne-r.ll'eigh out into a suitable cru cible: 8 parts grape sugar, 12 parts sulfur, parts sodium sulfid crystals. Apply and raise the temperature to 120 After one hour at this temperature dissolve in wasulfanilic acid. 'Raise the heat to drive off the water, then raise the heat gradually but" steadily to 150 180 (3., and heat until a dry powder is formed, or'a dyeing test of the fusion shows that the color has been fully formed. The above process gives the best result, although a similar result'is obtained.

heat

' ter, cool,and add 6 parts of sodium salt of by addingthe sodium salt of sulfanilic acid in the be 'nning. The resulting substance is soluble 1n cold water, coldsodium oarbonate solution, alcohol, and caustic alkaline so-' lution, and dyes unmordagnted cotton afast medium brown in a salt bath made alkaline with soda, with or without the addition'of sodium sulfid. It may also be concentrated in the usual'nianner by precipitation with hydrochloric acid, in which case the resulting substance will be insolublein cold water,

cold sodium carbonate solution, alcohol, and

concentratedsulfuric acid, slowly soluble in caustic alkaline solution and readily soluble in cold sodiumsulfid solution. It will dye unmordanted cotton a fast medium brown in v the usual alkaline saltbath, with the assistance of sodium sulfid. fVariations of temperature'will produce a variation in the shade of the product. By varying the proportion of the ingredient other variations in color can be'rproduced. Whenthe same operationis pe ormed without the grapesugar, no color is formed. This example llustrates a great number of syntheses of colorin matters that can be performed by the use 0 these univer-' sal colorformer's. Thus by substituting for the sodium salt .of sulfanilic acid in the above formula, eitheranilin salts, b'enzidin, or diphenylamin, chemicals which are not color formers, when sulfured other and new colors 1. The process of making coloring matters f consisting in heating asugar with sulfuringsubstances until a,non-hygroscopic, readily dyestufi is formed, substantially as described.

2. The process of ifiaking coloring matters: consisting in heating rape sugar with sulfuring substances,

non hygroscopic,

ran

I dyestufif isforsned, substanL-ially abs '1 3. a no" dark brown eoiozring matter which eon: be obtained, iron same wit-l1 sail in and sodium sulfid, which is non h-ygs osco iie, readily ulverizsble, solu andwalnf dyes cotton in an alkaline salt boil" 4 01' without the addition of sodium solid East dark-brown shades, and'which, when heated with hydrochloric acid forms a dark brown ooloring malaber which is insolum'tislo of manufacture, the

wraps sugar by heating the wsienoold so 7 um carbonate soeolci oi 'CZHISUG sods solution,-

ble in cold water, sodium carbonateso lntion, alcohol, and concentrated Sulfurio acid, is easily soluble in caustic alkaline solution, and readily soluble in cold sodium sullid solution, and dyes cotton from an alkaline salt bath with t? is assistance of sodium sulfid fest dark brbnrn sbedes.

In testimony whereof I have hereunto signed my name inthe presence of two subscribingxvitnesses.

' .EMILE THEODORE BUNDSMAN. Witnesses:

O. THU-RSTON, G, on PURUGKER. 

